Process for reactivating used catalysts



Aug. 31, 1943'. J. D. SEGUY PROCESS FOR REACTIVATING USED CATALYSTS Filed Aug. 15, 1940 f 6 M 7 rm. )1: 9/ m 0 7 C m o 1 GASES CONVERSION PROD UCTS INVENTOR. e444 %vo n Patented Aug. .31, 1943 UNITED, STATES PATENT OFFICE];

I PROCESS FOR REACTIVATING USED CAIIALYSTS Jean Delattre Seguy, Chicago, 111., assignor to Universal Oil Products Company, Chicago, 111., a corporation Delaware Application August 15, 1940; Serial No. 352,681 n 3 Claims. ((31. 196-552) This inventionrelates to improvements in the method of reactivating spent catalyst masses temperature, due to the fact that no preheating of the catalyst bed by hydrocarbon reactants upon which carbonaceous substances have deposited during a prior processing period and more specifically to a method of reactivation whereby.

the temperature of the catalyst mass after reactivation is substantially uniform throughout. In the reactivation of spent catalyst masses to remove carbonaceous substances which have deposited thereon during use in conversion of hydrocarbans, it is generally found that combustion of thesecarbonaceous substances, ,particu larly in relatively deep beds of catalytic material,

' will not take place throughout the entire bed at one time, but instead a relatively shallow burning zone passes through the bed of catalytic ma terial from inlet to outlet so that combustion is thereof, if one is employing a relatively low temperature on the inlet stream of reactivating gases the uppermost portions of the catalyst bed or inbed will beat'the higher peak reactivatin'g temperatures. When reactivation is completed then tion while the other part thereof will be' at a ing period, reversing the direction of flow of said 'reactivating gases after reactivation is substantaking place in only a relatively small portion of the catalyst bed in any given time. As a result would be necessary, as is usually the case in processes employing the usual method of reactivation, because inmy process the temperature in substantially all portions of the catalyst bed may be so controlled that it is substantially equal to the most desirable conversion temperature. In one specific embodiment the invention comprises passing a stream of heated oxygen-containing reactivating gases in contact with a bed of catalytic material to remove therefrom carbonaceous substances deposited during a prior processtially completed as evidenced by a drop in temperature to disperse the heat accumulated at the outlet of said'catalyst bed so that said catalyst.

bed is brought to a substantially uniform temperature throughout before hydrocarbon reactants are passed in contact therewith.

, tional side elevation of the apparatus which mayv as evidenced by a decline in the peak reactivat- I any specific type of catalytic reactionbut may,

temperature substantially equal to the inlet of' the reactivating gas stream, and I have found that the temperature difference existing between the inletand outlet of the catalyst bed may range from 100 to 200%. or more.

After completingreactivation, in the manner 7 above described, when hydrocarbon'reactants are supplied to the fr'eshly'reactivated bed of catalytlc material, it isapparent that conversion in the lower portion or' atthe outlet of the catalyst bed will in a' large extent *be 'due to thermal effects rather than the contemplated catalytic eflect.-

- In VieW-ofthe above, after Jreactivationhas' been completed. my, invention provides for revex-sing the direction of the flow of reactivating cases so that heat that has accumulated at the lower or outlet end of the catalyst'bed may be dispersed through the. rest 'ofthe catalyst bed lyreactivatod catalytic material at slower-inlet so whereby the inlet and outletportions thereof are I One specific method of accomplishing the objects of the invention will'be described while referring to the accompanying drawing, wherein, Fig. 1 is a diagrammatic illustration in convenbe employed,.while Figs. 2 and 2A are illustrations of four-way switching valves indicated as The invention is not limited with respect to find. greater vapplicability in catalytic processesv wherein the conversion reaction is endothermic such as, for example, catalytic cracking, dehylows will be limited to the use of the invention in a catalytic cracking process employing any of the well known types of catalytic material. Referring now to Fig. l, the apparatus is shown as consisting of .two reactors A and B which are equipped for alternate use in processing and reactivation.' The reactors may be ofthe conventional type comprising, for example, reactors in which the catalytic material is. contained in relatively small diameter tubes and wherein provisions are made for introducing a fluid heat conveotive medium to supply heat during conversion and withdraw heat during reactivation or, on the other hand, the reactors may comprise those of the type which contain relatively shallow beds of catalytic material wherein conversion and reactivation is accomplished-substantiallyadiabat ically. In the case such-as h re u trat d. with two reactors the stream of. reactants is introbe disposed'of in any desiredmanner.

duced to one reactor simultaneously with the introduction of a stream of reactivating gases to the other reactor, and provisions are made for alternately'switching the streams of reactants and ,reactivating gases .from one reactor to the other-and for switching the streams of used reactivating gases and I conversion I products. Switching of the various streams may be accomplished by any of the well known methods suchas, for example; by means of automatically. operated two-way valves, but for the purpose of this invention I have shown the switching valves as comprising four-way valves containing two passageways which may be switched. irom the 'position illustrated in Fig. 2 to that illustrated in Fig. 2A and vice versa.

Hydrocarbon reactants to be converted in'the process comprising, for example, a hydrocarbon oil amenable-to catalytic cracking are supplied through line I to valve VI. With reactor A on process valve VI which controls the direction of flow of the reactants and .fresh reactivating gases.

is adjusted to the position illustrated 2 while valve V2 which controls the dire on of flow of the reactants and used reactivating' gases and pass therethrough opposite to the direction in which thereactivating gases flowed while reactivation was being accomplished. manner, heat which has accumulated in the lower portion of the bed of catalyticmaterial in reactor B is dispersed throughout the other portions of the bed and the entire bed'is brought to a substantially uniform temperature throughout. The reactiva'ting gases introduced into the lower portion of reactor B are withdrawn there- I from by way of line 5, pass through valve VI into line 8, thence through valve V3 into line III, the. treatment being substantially as. described; However, in this case, the used gases are returned to the reactor and there is no need ior the introduction of oxygen as above mentioned I With reactor 13 on process the catalytic materrial in reactor A is undergoing reactivation and valves VI and V2 are adjusted to the positions previously mentioned while valve V3-is adjusted to the position illustrated. in Fig. 2. In this is adjusted to the position illustrated in Fig 2A.

Hydrocarbon reactants in line I therefor pass;

throughvalvevl into line 2 by means of which they are supplied to reactor A. The conversion 'supplied to reactor B. The conversion products leaving reactor B are directed through line 6 to valve V2 wherethrough they pass into line 4 and are thereafter subjected to treatment in the manner previously described.

- When reactor A is on process and the catalytic material in reactor B is undergoing reactivation valve V3 may be adjusted to the position illustrated in Fig. 2 in which case fresh reactivating -case,. fresh reactivating. gases in line 1 containing a controlled minor amount of oxygen are directed through valve V3 into line 8, theme through valve VI into line 2 by means of which they are supplied. to reactor A. Used reactivating gases leaving reactor A'are directed through line 3 to valve V2 wherethrough they pass intoline 9, thence through valve V3 into line I0, the flow thereafter being substantially as described. In this case, alsoJwhen reactivation has been.

substantially accomplished in reactor A valve V3 is" switched to the positionillustrated in Fig. 2A whereupon fresh reactivating gases in line I,

preferably containing substantially no oxygen,

pass through valve V3 into line 9, thence through- I valve V2 into line 3 by means of whichthey are introduced into the lower portion of reactor A.

These reactivating gases in passing through re- I actor A-disperse the' heat accumulated at the lower portion thereof throughout substantially the whole of the catalyst bed and the gases leaving this reactor are directed through line 2 .to valve VI wherethrough they pass, into line 8, theme through valve V3 into'line I0, after which they may be disposed of or used in any desired manner as above mentioned.

gases comprising, for example, combustion gases containing controlled minor amounts of oxygen supplied by way of line I are directed through valve V3 .into line. 8, pass through valve VI into linei, and thence into reactor 13. Combustion products and used reactivatlng gases leaving reactor B are directed through line 5 to valve V2 wherethrough they pass into line 9, thence through valve 'V3.into line I0 and, when desired,

'a portion thereotmay be cooledjthe oxygen replenished, and this porti onreturned as the fresh reactivating gases or. the whole or a part may After reactivation has been substantially completed in reactor B as evidenced by a drop in the peak reactivating. temperature or as shown by an oxygen analysis or the used 'reactivating gases The following is an example of what may be accomplished in conducting thereactivation of a bed of used silica-alumina catalyst as above de- "scribed. I

A bed of silica-alumina catalyst approximately 2 feet in thickness is reactivatedby passing a stream of reactivating gases heated to a temper.-

ature of approximately 850 F. and containing approximately 2% oxygen in contact therewith.

' Peak reactivating'temperatures-in this operation (i. e., when no more oxygen is consumed in the 1 reaction), valve V3 may be switched to the position' illustrated in'Flg. 2A and preferably also the oxygen supply is stopped whereupon the gases in linel containing substantially noor only a relatively small. proportion of oxygen pass through valve V3 into line 9, thence through v valve V2 into line i by means of'which theyare introduced into the lowerv portion or reactor B 7.

' are preferably controlled so that they'- do not "exceed approximately 1300 F. After reactivation is substantially complete, as evidencedby a rather rapid drop' in temperature'from the peak reactivating temperature or say 1300",F. to about 1100' F5, .the temperature at the inlet of the catalyst bed was approximately 870F., that at the middle approximately 900 F., as above mentioned, and that at the outlet 1100 F. Inaccordance with the objects of the invention,. the direction of now of reactivating gases was reversed and after ap proximately 5 minutes the temperature difleren'ce from top to bottom was not more. than 20 with h a mean-average temperature of approximately In this' It is understood that my invention is broadly.

concerned with a method of obtaining an equal distribution of heat and an even temperature as near as possible equal to that desired for the reaction, throughout the catalyst bed after reactivation but prior to its use as a reacting catalyst. While I have more specifically described my invention in connection with a process in which the flow of reactivating gas is reversed for the p rpose set forth above, it. should be understood that a substantially inert gas from any source may be substituted for the reactivating gas for the purpose of distributing heat in the catalyst bed. The substituted gas is preferably preheated and used in an amount suiilcient to obviate long conditioning periods.

I claim as my invention:

1. In a catalytic conversion process employlngbeds of catalytic material alternately processed and reactivated, reactivation being accomplished y Passing a heated stream of oxygencontainlng reactivating gases in contact with said beds to burn therefrom carbonaceous substances deposited during a prior processing period, the improvement which comprises stopping the flow of reactivating gases after reactivation is sub-' stantially completed and passing a stream of substantially inert gases opposite to the direction of flow of said reactivating gases for a time period sufflcient to substantially uniformly distribute heat accumulatedat the outlet of said bed through other portions thereof.

2. In a catalytic conversion process employing beds of catalytic material alternately processed and reactivated, reactivation being accomplished by passing a heated stream of reactivating gases containing controlled minor amounts of oxygen incontact with saidbeds tobumtherei'rom carbonaceous substances depositedduring-aprior processing period, the improvement which comprisesstomflngtbeiniectionotwminsaid' reactivating gas after reactivation issubfiantially completed and passing the substantially oxygen-free gasesin contact with the bed of cat-- similar bed of catalytic material to burn therefrom carbonaceous substances deposited during a prior processing period and wherein provisions are made for alternately processing and reactivating the separate beds of catalytic material, the improvement which comprises stoppingthe iniection of oxygen in the reactivating gases charged to the bed of catalyst undergoing reactivation when reactivation is substantially completed, passing the oxygen-free gases in contact with the reactivated bed in a direction opposite to the direction of flow of said reactivating gases and for a period of time suflicient to substantially uniformly distribute heat accumulated at the outlet of the bed through other portions thereof.

' JEAN DELATI'RE SEGUY. 

